N-(substituted)-5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2h)-carboxylate derivatives

ABSTRACT

This present disclosure is related to the field of N-(substituted)-5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxylates and their derivatives and to the use of these compounds as fungicides. Also provided are methods of controlling a fungal disease such as  Septoria tritici , comprising administering an effective amount of the fungicide compound to at lease one surface associated with the plant, seed or soil.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/747,086 filed Dec. 28, 2012, which is expresslyincorporated by reference herein.

BACKGROUND AND SUMMARY OF THE INVENTION

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

The present disclosure relates toN-(substituted)-5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxylatecompounds and their use as fungicides. The compounds of the presentdisclosure may offer protection against fungi and fungi like organismsincluding ascomycetes, basidiomycetes, deuteromycetes, and oomycetes.

One embodiment of the present disclosure may include compounds ofFormula I:

wherein R¹ is —C(═O)OR⁴ or —C(═S)OR⁴;

R² is C₁-C₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆ haloalkyl, C₁-C₆alkoxyalkyl, C₁-C₆ aminoalkyl, C₂-C₆ alkylcarbonyl, arylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, —S(O)₂R⁵, phenyl or benzylwherein each of the phenyl or the benzyl may be optionally substitutedwith 1-3 R⁵, or a 5- or 6-membered saturated or unsaturated ringcontaining 1-3 heteroatoms wherein each ring may be optionallysubstituted with 1-3 R⁵;

R³ is independently H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, arylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, phenyl or benzyl wherein eachof the phenyl or the benzyl may be optionally substituted with 1-3 R⁵,or a 5- or 6-membered saturated or unsaturated ring containing 1-3heteroatoms, wherein each ring may be optionally substituted with 1-3R⁵;

R⁴ is independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl,C₂-C₆ alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or thebenzyl may be optionally substituted with 1-3 R⁵, or a 5- or 6-memberedsaturated or unsaturated ring containing 1-3 heteroatoms, wherein eachring may be optionally substituted with 1-3 R⁵;

R⁵ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy,C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, amino, C₁-C₆alkylamino, C₂-C₆ alkoxycarbonyl, or C₂-C₆ alkylcarbonyl, cyano, ornitro.

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described below and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the step of applying a fungicidally effective amount of one ormore of the compounds described below to at least one of the fungus, theplant, an area adjacent to the plant, or the seed adapted to produce theplant.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the step of applying a fungicidally effective amount of one ormore of the compounds described below to at least one of the fungus, theplant, an area adjacent to the plant, or the seed adapted to produce theplant.

Still another embodiment is a composition for the control of a fungaldisease, a comprising a composition for the control of at least onefungal disease, said composition including a fungicidally effectiveamount of the compound of Formula I and a phytologically acceptablecarrier material. In some embodiments the fungal disease is selectedfrom the group of organisms consisting of: Venturia inaequalis, Septoriatritici, Cercospora beticola, Cercospora arachidicola, CercosporidiumpersonatumI, and Mycosphaerella fijiensis.

Still other embodiments include methods for the control and preventionof fungal attack on a plant, the method including the steps of: applyinga fungicidally effective amount of at least one of the compounds ofFormula 1 to at least one surface selected from the group of surfacesselected from the group consisting of: a portion of a plant, an areaadjacent to a plant, soil in contact with a plant, soil adjacent to aplant, any surface adjacent to a plant, any surface in contact with aplant, a seed, and equipment used in agriculture. In some embodiments afungicidally effective amount of Formula I is applied in the range ofabout 0.01 g/m² to about 0.45 g/m² of Formula I.

The term “alkyl” refers to a branched, unbranched, or cyclic carbonchain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl,tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and the like.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds, including ethenyl, propenyl,butenyl, isopropenyl, isobutenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chaincontaining one or more triple bonds, including propynyl, butynyl and thelike.

As used throughout this specification, the term ‘R’ refers to the groupconsisting of C₁₋₈ alkyl, C₃₋₈ alkenyl or C₃₋₈ alkynyl, unless statedotherwise.

The term “alkoxy” refers to an —OR substituent.

The term “alkoxycarbonyl” refers to a —C(O)—OR substituent.

The term “alkylcarbonyl” refers to a —C(O)—R substituent.

The term “arylcarbonyl” refers to a —C(O)—R substituent, where R iseither phenyl, wherein the phenyl may be optionally substituted with 1-3R⁵, or a 5- or 6-membered saturated or unsaturated ring containing 1-3heteroatoms, wherein each ring may be optionally substituted with 1-3R⁵.

The term “alkylsulfonyl” refers to an —SO₂—R substituent.

The term “alkylthio” refers to an —S—R substituent.

The term “halothio” refers to a sulfur substituted with three or five Fsubstituents.

The term “haloalkylthio” refers to an alkylthio, which is substitutedwith Cl, F, I, or Br or any combination thereof

The term “alkylaminocarbonyl” refers to a —C(O)—N(H)—R substituent.

The term “trialkylsilyl” refers to —SiR₃.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “amino” refers to a —NH₂ substituent.

The term “alkylamino” refers to a —N(H)—R substituent.

The term “dialkylamino” refers to a —NR₂ substituent.

The term “alkoxyalkyl” refers to an alkoxy substitution on an alkyl.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

Unless specifically noted or clearly implied otherwise the term “about”refers to a range of values of plus or minus 10 percent, e.g. about 1refers to the range 0.9 to 1.1.

Throughout the disclosure, reference to the compounds of Formula I isread as also including optical isomers and salts of Formula I, andhydrates thereof. Specifically, when Formula I contains a branched chainalkyl group, it is understood that such compounds include opticalisomers and racemates thereof. Exemplary salts include: hydrochloride,hydrobromide, hydroiodide, and the like. Additionally, the compounds ofFormula I may include tautomeric forms.

Certain compounds disclosed in this document can exist as one or moreisomers. It will be appreciated by those skilled in the art that oneisomer may be more active than the others. The structures disclosed inthe present disclosure are drawn in only one geometric form for clarity,but are intended to represent all geometric and tautomeric forms of themolecule.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or seeds.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

Additional features and advantages of the present invention will becomeapparent to those skilled in the art upon consideration of the followingdetailed description of the illustrative embodiments exemplifying thebest mode of carrying out the invention as presently perceived.

DETAILED DESCRIPTION OF THE DISCLOSURE

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots, seeds or foliage of plants for the control of various fungi,without damaging the commercial value of the plants. The materials maybe applied in the form of any of the generally used formulation types,for example, as solutions, dusts, wettable powders, flowableconcentrates, suspension concentrates or emulsifiable concentrates.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble,water-suspendible, or emulsifiable formulations which are solids,usually known as wettable powders; or liquids, usually known asemulsifiable concentrates, aqueous suspensions, or suspensionconcentrates. As will be readily appreciated, any material to whichthese compounds may be added may be used, provided it yields the desiredutility without significant interference with the activity of thesecompounds as antifungal agents.

Wettable powders, which may be compacted to form water dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 10 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanol.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulfonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present invention arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, the methyl ether of triethylene glycol,petroleum fractions or hydrocarbons such as mineral oil, aromaticsolvents, paraffinic oils, and the like; vegetable oils such as soybeanoil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconutoil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil,safflower oil, sesame oil, tung oil and the like; esters of the abovevegetable oils; and the like. Mixtures of two or more organic liquidsmay also be employed in the preparation of the emulsifiable concentrate.Organic liquids include xylene, and propyl benzene fractions, withxylene being most preferred in some cases. Surface-active dispersingagents are typically employed in liquid formulations and in an amount offrom 0.1 to 20 percent by weight based on the combined weight of thedispersing agent with one or more of the compounds. The formulations canalso contain other compatible additives, for example, plant growthregulators and other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 5 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle. It is often most effective to grind and mix at the same time bypreparing the aqueous mixture and homogenizing it in an implement suchas a sand mill, ball mill, or piston-type homogenizer.

Aqueous emulsions comprise emulsions of one or more water-insolublepesticidally active ingredients emulsified in an aqueous vehicle at aconcentration typically in the range from about 5 to about 50 weightpercent, based on the total weight of the aqueous emulsion. If thepesticidally active ingredient is a solid it must be dissolved in asuitable water-immiscible solvent prior to the preparation of theaqueous emulsion. Emulsions are prepared by emulsifying the liquidpesticidally active ingredient or water-immiscible solution thereof intoan aqueous medium typically with inclusion of surfactants that aid inthe formation and stabilization of the emulsion as described above. Thisis often accomplished with the aid of vigorous mixing provided by highshear mixers or homogenizers.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent. Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulfosuccinic acids, ethoxylated organosilicones,ethoxylated fatty amines, blends of surfactants with mineral orvegetable oils, crop oil concentrate (mineral oil (85%)+emulsifiers(15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternaryammonium salt; blend of petroleum hydrocarbon, alkyl esters, organicacid, and anionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphatedalcohol ethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate;di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;nonylphenol ethoxylate+urea ammonium nitrrate; emulsified methylatedseed oil; tridecyl alcohol (synthetic) ethoxylate (8EO); tallow amineethoxylate (15 EO); PEG(400) dioleate-99. The formulations may alsoinclude oil-in-water emulsions such as those disclosed in U.S. patentapplication Ser. No. 11/495,228, the disclosure of which is expresslyincorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to 100:1.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank-mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude (RS)—N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme,N-3,5-dichlorophenyl-succinimide, N-3-nitrophenylitaconimide,2-(thiocyanatomethylthio)-benzothiazole, (3-ethoxypropyl)mercurybromide, 2-methoxyethylmercury chloride, 2-phenylphenol,8-hydroxyquinoline sulfate, 8-phenylmercurioxyquinoline, acibenzolar,acibenzolar-S-methyl, acypetacs, acypetacs-copper, acypetacs-zinc,albendazole, aldimorph, allicin, allyl alcohol, ametoctradin,amisulbrom, amobam, Ampelomyces quisqualis, ampropylfos, anilazine,antimycin, asomate, aureofungin, azaconazole, azithiram, azoxystrobin,Bacillus subtilis, Bacillus subtilis strain QST713, barium polysulfide,Bayer 32394, benalaxyl, benalaxyl-M, benquinox, benodanil, benomyl,bentaluron, benthiavalicarb, benthiavalicarb-isopropyl, benthiazole,benzamacril, benzamacril-isobutyl, benzamorf, benzohydroxamic acid,benzovindiflupyr, benzylaminobenzene-sulfonate (BABS) salt, berberine,berberine chloride, bethoxazin, bicarbonates, bifujunzhi, binapacryl,biphenyl, bismerthiazol, bis(methylmercury) sulfate, bis(tributyltin)oxide, bitertanol, bithionol, bixafen, blasticidin-S, borax, Bordeauxmixture, boscalid, bromothalonil, bromuconazole, bupirimate, Burgundymixture, buthiobate, butylamine, cadmium calcium copper zinc chromatesulfate, calcium polysulfide, Candida oleophila, captafol, captan,carbamorph, carbendazim, carbendazim benzenesulfonate, carbendazimsulfite, carboxin, carpropamid, carvacrol, carvone, CECA, Cheshuntmixture, chinomethionat, chitosan, chlazafenone, chlobenthiazone,chloraniformethan, chloranil, chlorfenazole, chlorodinitronaphthalenes,chlorquinox, chloroneb, chloropicrin, chlorothalonil, chlozolinate,climbazole, clotrimazole, Coniothyrium minitans, copper acetate, copperbis(3-phenylsalicylate), copper carbonate, basic, copper hydroxide,copper naphthenate, copper octanoate, copper oleate, copper oxychloride,copper silicate, copper sulfate, copper sulfate (tribasic), copper zincchromate, coumoxystrobin, cresol, cufraneb, cupric hydrazinium sulfate,cuprobam, cuprous oxide, cyazofamid, cyclafuramid, cycloheximide,cyflufenamid, cymoxanil, cypendazole, cyproconazole, cyprodinil,cyprofuram, dazomet, dazomet-sodium, DBCP, debacarb, decafentin,dehydroacetic acid, diammonium ethylenebis-(dithiocarbamate),dichlofluanid, dichlone, dichloran, dichlorophen, dichlozoline,diclobutrazol, diclocymet, diclomezine, diclomezine-sodium,diethofencarb, diethyl pyrocarbonate, difenoconazole, difenzoquat ion,diflumetorim, dimetachlone, dimethirimol, dimethomorph, dimoxystrobin,dingjunezuo, diniconazole, diniconazole-M, dinobuton, dinocap,dinocap-4, dinocap-6, dinocton, dinopenton, dinosulfon, dinoterbon,diphenylamine, dipyrithione, disulfiram, ditalimfos, dithianon,dithioether, DNOC, DNOC-ammonium, DNOC-potassium, DNOC-sodium,dodemorph, dodemorph acetate, dodicin, dodicin hydrochloride,dodicin-sodium, dodine, dodine free base, drazoxolon, EBP, edifenphos,enestrobin, enestroburin, enoxastrobin, epoxiconazole, ESBP,etaconazole, etem, ethaboxam, ethirim, ethirimol, ethoxyquin, ethirimol,ethylmercury 2,3-dihydroxypropyl mercaptide, ethylmercury acetate,ethylmercury bromide, ethylmercury chloride, ethylmercury phosphate,etridiazole, famoxadone, fenamidone, fenaminosulf, fenaminstrobin,fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan,fenjuntong, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph,fenpyrazamine, fentin, fentin acetate, fentin chloride, fentinhydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin,flumetover, flumorph, fluopicolide, fluopyram, fluoroimide,fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, fluthiacet-methyl, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, furcarbanil, furconazole,furconazole-cis, furfural, furmecyclox, furophanate, Fusarium oxysporum,Gliocladium spp., glyodine, griseofulvin, guazatine, guazatine acetates,GY-81, halacrinate, Hercules 3944, hexachlorobenzene,hexachlorobutadiene, hexachlorophene, hexaconazole, hexylthiofos,huanjunzuo, hydrargaphen, hymexazol, ICIA0858, imazalil, imazalilnitrate, imazalil sulfate, imibenconazole, iminoctadine, iminoctadinetriacetate, iminoctadine tris(albesilate), inezin, iodocarb,iodomethane, ipconazole, ipfenpyrazolone, iprobenfos, iprodione,iprovalicarb, isopamphos, isoprothiolane, isopyrazam, isotianil,isovaledione, jiaxiangjunzhi, kasugamycin, kasugamycin hydrochloridehydrate, kejunlin, kresoxim-methyl, laminarin, lvdingjunzhi, mancopper,mancozeb, mandipropamid, maneb, mebenil, mecarbinzid, mefenoxam,mepanipyrim, mepronil, meptyl-dinocap, mercuric chloride, mercuricoxide, mercurous chloride, metalaxyl, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metazoxolon, metconazole,methasulfocarb, methfuroxam, methyl bromide, methyl iodide, methylisothiocyanate, methylmercury benzoate, methylmercury dicyandiamide,methylmercury pentachlorophenoxide, metiram, metominostrobin,metrafenone, metsulfovax, mildiomycin, milneb, moroxydine, moroxydinehydrochloride, mucochloric anhydride, myclobutanil, myclozolin,N-ethylmercurio-4-toluenesulfonanilide,N-(ethylmercury)-p-toluenesulphonanilide, nabam, natamycin, nickelbis(dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl,nuarimol, OCH, octhilinone, ofurace, oleic acid (fatty acids),orysastrobin, osthol, oxadixyl, oxathiapiprolin, oxine-copper,oxpoconazole fumarate, oxycarboxin, parinol, pefurazoate, penconazole,pencycuron, penflufen, pentachlorophenol, pentachlorophenyl laurate,penthiopyrad, phenamacril, phenylmercuriurea, phenylmercury acetate,phenylmercury chloride, phenylmercury derivative of pyrocatechol,phenylmercury dimethyldithiocarbamate, phenylmercury nitrate,phenylmercury salicylate, Phlebiopsis gigantea, phosdiphen, phosphonicacid, phthalide, picoxystrobin, piperalin, polycarbamate, polyoxin B,polyoxins, polyoxorim, polyoxorim-zinc, potassium azide, potassiumbicarbonate, potassium hydroxyquinoline sulfate, potassium polysulfide,potassium thiocyanate, probenazole, prochloraz, prochloraz-manganese,procymidone, propamidine, propamidine dihydrochloride, propamocarb,propamocarb hydrochloride, propiconazole, propineb, proquinazid,prothiocarb, prothiocarb hydrochloride, prothioconazole, pyracarbolid,pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos,pyribencarb, pyributicarb, pyridinitril, pyrifenox, pyrimethanil,pyriofenone, pyrisoxazole, pyroquilon, pyroxychlor, pyroxyfur,quinacetol, quinacetol sulfate, quinazamid, quinoclamine, quinconazole,quinoxyfen, quintozene, rabenzazole, Reynoutria sachalinensis extract,saisentong, salicylanilide, santonin, sedaxane, silthiofam,simeconazole, sodium 2-phenylphenoxide, sodium azide, sodiumbicarbonate, sodium orthophenylphenoxide, sodium pentachlorophenoxide,sodium polysulfide, spiroxamine, Streptomyces griseoviridis,streptomycin, streptomycin sesquisulfate, SSF-109, sulfur, sultropen,SYP-Z048, tar oils, tebuconazole, tebufloquin, tecloftalam, tecnazene,tecoram, tetraconazole, thiabendazole, thiadifluor, thicyofen,thifluzamide, thiochlorfenphim, thiodiazole-copper, thiomersal,thiophanate, thiophanate-methyl, thioquinox, thiram, tiadinil, tioxymid,tolclofos-methyl, tolylfluanid, tolylmercury acetate, triadimefon,triadimenol, triamiphos, triarimol, triazbutil, triazoxide, tributyltinoxide, trichlamide, triclopyricarb, Trichoderma spp., tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,uniconazole, uniconazole-P, urbacid, validamycin, valifenalate,valiphenal, vangard, vinclozolin, xiwojunan, zarilamid, zineb, zincnaphthenate, zinc thiazole, ziram, and zoxamide, and any combinationsthereof.

Additionally, the compounds of the present invention may be combinedwith other pesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: 1,2-dichloropropane, abamectin, acephate,acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin,allyxycarb, alpha-cypermethrin, alpha-ecdysone, alpha-endosulfan,amidithion, aminocarb, amiton, amiton oxalate, amitraz, anabasine,athidathion, azadirachtin, azamethiphos, azinphos-ethyl,azinphos-methyl, azothoate, barium hexafluorosilicate, barthrin,bendiocarb, benfuracarb, bensultap, beta-cyfluthrin, beta-cypermethrin,bifenthrin, bioallethrin, bioethanomethrin, biopermethrin, bistrifluron,borax, boric acid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos,bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos,butocarboxim, butonate, butoxycarboxim, cadusafos, calcium arsenate,calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran,carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan,cartap, cartap hydrochloride, chlorantraniliprole, chlorbicyclen,chlordane, chlordecone, chlordimeform, chlordimeform hydrochloride,chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron,chlormephos, chloroform, chloropicrin, chlorphoxim, chlorprazophos,chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide,cinerin I, cinerin II, cinerins, cismethrin, cloethocarb, closantel,clothianidin, copper acetoarsenite, copper arsenate, copper naphthenate,copper oleate, coumaphos, coumithoate, crotamiton, crotoxyphos,crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate,cyantraniliprole, cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin,cypermethrin, cyphenothrin, cyromazine, cythioate, DDT, decarbofuran,deltamethrin, demephion, demephion-O, demephion-S, demeton,demeton-methyl, demeton-O, demeton-O-methyl, demeton-S,demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos,diatomaceous earth, diazinon, dicapthon, dichlofenthion, dichlorvos,dicresyl, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dilor,dimefluthrin, dimefox, dimetan, dimethoate, dimethrin, dimethylvinphos,dimetilan, dinex, dinex-diclexine, dinoprop, dinosam, dinotefuran,diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton,dithicrofos, d-limonene, DNOC, DNOC-ammonium, DNOC-potassium,DNOC-sodium, doramectin, ecdysterone, emamectin, emamectin benzoate,EMPC, empenthrin, endosulfan, endothion, endrin, EPN, epofenonane,eprinomectin, esdepalléthrine, esfenvalerate, etaphos, ethiofencarb,ethion, ethiprole, ethoate-methyl, ethoprophos, ethyl formate,ethyl-DDD, ethylene dibromide, ethylene dichloride, ethylene oxide,etofenprox, etrimfos, EXD, famphur, fenamiphos, fenazaflor,fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb,fenoxacrim, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion,fenthion, fenthion-ethyl, fenvalerate, fipronil, flonicamid,flubendiamide, flucofuron, flucycloxuron, flucythrinate, flufenerim,flufenoxuron, flufenprox, flufiprole, fluvalinate, fonofos, formetanate,formetanate hydrochloride, formothion, formparanate, formparanatehydrochloride, fosmethilan, fospirate, fosthietan, furathiocarb,furethrin, gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH,HEOD, heptachlor, heptenophos, heterophos, hexaflumuron, HHDN,hydramethylnon, hydrogen cyanide, hydroprene, hyquincarb, imidacloprid,imiprothrin, indoxacarb, iodomethane, IPSP, isazofos, isobenzan,isocarbophos, isodrin, isofenphos, isofenphos-methyl, isoprocarb,isoprothiolane, isothioate, isoxathion, ivermectin, jasmolin I, jasmolinII, jodfenphos, juvenile hormone I, juvenile hormone II, juvenilehormone III, kelevan, kinoprene, lambda-cyhalothrin, lead arsenate,lepimectin, leptophos, lindane, lirimfos, lufenuron, lythidathion,malathion, malonoben, mazidox, mecarbam, mecarphon, menazon,meperfluthrin, mephosfolan, mercurous chloride, mesulfenfos,metaflumizone, methacrifos, methamidophos, methidathion, methiocarb,methocrotophos, methomyl, methoprene, methoxychlor, methoxyfenozide,methyl bromide, methyl isothiocyanate, methylchloroform, methylenechloride, metofluthrin, metolcarb, metoxadiazone, mevinphos,mexacarbate, milbemectin, milbemycin oxime, mipafox, mirex, molosultap,monocrotophos, monomehypo, monosultap, morphothion, moxidectin,naftalofos, naled, naphthalene, nicotine, nifluridide, nitenpyram,nithiazine, nitrilacarb, novaluron, noviflumuron, omethoate, oxamyl,oxydemeton-methyl, oxydeprofos, oxydisulfoton, para-dichlorobenzene,parathion, parathion-methyl, penfluron, pentachlorophenol, permethrin,phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan,phosmet, phosnichlor, phosphamidon, phosphine, phoxim, phoxim-methyl,pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassiumarsenite, potassium thiocyanate, pp′-DDT, prallethrin, precocene I,precocene II, precocene III, primidophos, profenofos, profluralin,promacyl, promecarb, propaphos, propetamphos, propoxur, prothidathion,prothiofos, prothoate, protrifenbute, pyraclofos, pyrafluprole,pyrazophos, pyresmethrin, pyrethrin I, pyrethrin II, pyrethrins,pyridaben, pyridalyl, pyridaphenthion, pyrifluquinazon, pyrimidifen,pyrimitate, pyriprole, pyriproxyfen, quassia, quinalphos,quinalphos-methyl, quinothion, rafoxanide, resmethrin, rotenone, ryania,sabadilla, schradan, selamectin, silafluofen, silica gel, sodiumarsenite, sodium fluoride, sodium hexafluorosilicate, sodiumthiocyanate, sophamide, spinetoram, spinosad, spiromesifen,spirotetramat, sulcofuron, sulcofuron-sodium, sulfluramid, sulfotep,sulfoxaflor, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb,TDE, tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron,tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, tetramethylfluthrin,theta-cypermethrin, thiacloprid, thiamethoxam, thicrofos, thiocarboxime,thiocyclam, thiocyclam oxalate, thiodicarb, thiofanox, thiometon,thiosultap, thiosultap-disodium, thiosultap-monosodium, thuringiensin,tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triarathene,triazamate, triazophos, trichlorfon, trichlormetaphos-3, trichloronat,trifenofos, triflumuron, trimethacarb, triprene, vamidothion,vaniliprole, XMC, xylylcarb, zeta-cypermethrin, zolaprofos, and anycombinations thereof.

Additionally, the compounds of the present invention may be combinedwith herbicides that are compatible with the compounds of the presentinvention in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: 4-CPA; 4-CPB; 4-CPP; 2,4-D; 2,4-D choline salt, 2,4-Desters and amines; 2,4-DB; 3,4-DA; 3,4-DB; 2,4-DEB; 2,4-DEP; 3,4-DP;2,3,6-TBA; 2,4,5-T; 2,4,5-TB; acetochlor, acifluorfen, aclonifen,acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorac,ametridione, ametryn, amibuzin, amicarbazone, amidosulfuron,aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrole, ammoniumsulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin,azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin,bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide,benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram,benzobicyclon, benzofenap, benzofluor, benzoylprop, benzthiazuron,bicyclopyrone, bifenox, bilanafos, bispyribac-sodium, borax, bromacil,bromobonil, bromobutide, bromofenoxim, bromoxynil, brompyrazon,butachlor, butafenacil, butamifos, butenachlor, buthidazole, buthiuron,butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrole,calcium chlorate, calcium cyanamide, cambendichlor, carbasulam,carbetamide, carboxazole chlorprocarb, carfentrazone-ethyl, CDEA, CEPC,chlomethoxyfen, chloramben, chloranocryl, chlorazifop, chlorazine,chlorbromuron, chlorbufam, chloreturon, chlorfenac, chlorfenprop,chlorflurazole, chlorflurenol, chloridazon, chlorimuron, chlornitrofen,chloropon, chlorotoluron, chloroxuron, chloroxynil, chlorpropham,chlorsulfuron, chlorthal, chlorthiamid, cinidon-ethyl, cinmethylin,cinosulfuron, cisanilide, clethodim, cliodinate, clodinafop-propargyl,clofop, clomazone, clomeprop, cloprop, cloproxydim, clopyralid,cloransulam-methyl, CMA, copper sulfate, CPMF, CPPC, credazine, cresol,cumyluron, cyanatryn, cyanazine, cycloate, cyclosulfamuron, cycloxydim,cycluron, cyhalofop-butyl, cyperquat, cyprazine, cyprazole, cypromid,daimuron, dalapon, dazomet, delachlor, desmedipham, desmetryn,di-allate, dicamba, dichlobenil, dichloralurea, dichlormate,dichlorprop, dichlorprop-P, diclofop, diclosulam, diethamquat,diethatyl, difenopenten, difenoxuron, difenzoquat, diflufenican,diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn,dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine,dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid,dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP,eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin,ethbenzamide, ethametsulfuron, ethidimuron, ethiolate, ethobenzamid,etobenzamid, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen,etnipromid, etobenzanid, EXD, fenasulam, fenoprop, fenoxaprop,fenoxaprop-P-ethyl, fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone,fenteracol, fenthiaprop, fentrazamide, fenuron, ferrous sulfate,flamprop, flamprop-M, flazasulfuron, florasulam, fluazifop,fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron,fluchloralin, flufenacet, flufenican, flufenpyr-ethyl, flumetsulam,flumezin, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron,fluorodifen, fluoroglycofen, fluoromidine, fluoronitrofen, fluothiuron,flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone,flurochloridone, fluroxypyr, flurtamone, fluthiacet, fomesafen,foramsulfuron, fosamine, furyloxyfen, glufosinate, glufosinate-ammonium,glyphosate, halauxifen, halosafen, halosulfuron-methyl, haloxydine,haloxyfop-methyl, haloxyfop-P-methyl, hexachloroacetone, hexaflurate,hexazinone, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, indanofan, indaziflam, iodobonil,iodomethane, iodosulfuron, iofensulfuron, ioxynil, ipazine,ipfencarbazone, iprymidam, isocarbamid, isocil, isomethiozin,isonoruron, isopolinate, isopropalin, isoproturon, isouron, isoxaben,isoxachlortole, isoxaflutole, isoxapyrifop, karbutilate, ketospiradox,lactofen, lenacil, linuron, MAA, MAMA, MCPA, esters and amines,MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet,mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, metamifop,metamitron, metazachlor, metazosulfuron, metflurazon,methabenzthiazuron, methalpropalin, methazole, methiobencarb,methiozolin, methiuron, methometon, methoprotryne, methyl bromide,methyl isothiocyanate, methyldymron, metobenzuron, metobromuron,metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, molinate,monalide, monisouron, monochloroacetic acid, monolinuron, monuron,morfamquat, MSMA, naproanilide, napropamide, naptalam, neburon,nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrofluorfen,norflurazon, noruron, OCH, orbencarb, ortho-dichlorobenzene,orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapyrazon,oxasulfuron, oxaziclomefone, oxyfluorfen, paraflufen-ethyl, parafluron,paraquat, pebulate, pelargonic acid, pendimethalin, penoxsulam,pentachlorophenol, pentanochlor, pentoxazone, perfluidone, pethoxamid,phenisopham, phenmedipham, phenmedipham-ethyl, phenobenzuron,phenylmercury acetate, picloram, picolinafen, pinoxaden, piperophos,potassium arsenite, potassium azide, potassium cyanate, pretilachlor,primisulfuron-methyl, procyazine, prodiamine, profluazol, profluralin,profoxydim, proglinazine, prohexadione-calcium, prometon, prometryn,propachlor, propanil, propaquizafop, propazine, propham, propisochlor,propoxycarbazone, propyrisulfuron, propyzamide, prosulfalin,prosulfocarb, prosulfuron, proxan, prynachlor, pydanon, pyraclonil,pyraflufen, pyrasulfotole, pyrazogyl, pyrazolynate,pyrazosulfuron-ethyl, pyrazoxyfen, pyribenzoxim, pyributicarb, pyriclor,pyridafol, pyridate, pyriftalid, pyriminobac, pyrimisulfan,pyrithiobac-methyl, pyroxasulfone, pyroxsulam, quinclorac, quinmerac,quinoclamine, quinonamid, quizalofop, quizalofop-P-ethyl, rhodethanil,rimsulfuron, saflufenacil, S-metolachlor, sebuthylazine, secbumeton,sethoxydim, siduron, simazine, simeton, simetryn, SMA, sodium arsenite,sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone,sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapin,swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione,tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton,terbuthylazine, terbutryn, tetrafluron, thenylchlor, thiazafluron,thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl,thifensulfuron, thiobencarb, tiocarbazil, tioclorim, topramezone,tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam,tribenuron, tricamba, triclopyr esters and amines, tridiphane,trietazine, trifloxysulfuron, trifluralin, triflusulfuron, trifop,trifopsime, trihydroxytriazine, trimeturon, tripropindan, tritac,tritosulfuron, vernolate and xylachlor.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, seed or locus of the fungus, or to a locusin which the infestation is to be prevented (for example applying tocereal plants), a fungicidally effective amount of one or more of thecompounds of Formula I. The compounds are suitable for treatment ofvarious plants at fungicidal levels, while exhibiting low phytotoxicity.The compounds may be useful both in a protectant and/or an eradicantfashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants. Additional benefits may include, but are not limited to,improving the health of a plant; improving the yield of a plant (e.g.increased biomass and/or increased content of valuable ingredients);improving the vigor of a plant (e.g. improved plant growth and/orgreener leaves); improving the quality of a plant (e.g. improved contentor composition of certain ingredients); and improving the tolerance toabiotic and/or biotic stress of the plant.

It will be understood by those in the art that the efficacy of thecompound for the foregoing fungi establishes the general utility of thecompounds as fungicides.

The compounds have broad ranges of activity against fungal pathogens.Exemplary pathogens may include, but are not limited to, wheat leafblotch (Mycosphaerella graminicola; anamorph: Septoria tritici), applescab (Venturia inaequalis), and Cercospora leaf spots of sugar beets(Cercospora beticola), leaf spots of peanut (Cercospora arachidicola andCercosporidium personatum), and black sigatoka of bananas(Mycosphaerella fijiensis). The exact amount of the active material tobe applied is dependent not only on the specific active material beingapplied, but also on the particular action desired, the fungal speciesto be controlled, and the stage of growth thereof, as well as the partof the plant or other product to be contacted with the compound. Thus,all the compounds, and formulations containing the same, may not beequally effective at similar concentrations or against the same fungalspecies.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact amount of a compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²). Fungicidally effective amount of the compounds includeamounts sufficient to kill or control true fungi, pseudo-fungi, andrelated organisms including water moulds.

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures.

The following examples are presented to illustrate the various aspectsof the compounds of the present disclosure and should not be construedas limitations to the claims.

Example 1 Preparation of5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one

Step 1: Preparation of4-Amino-5-fluoro-1-(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one (I-1)

To commercially available 4-amino-5-fluoro-pyrimidin-2-ol (1.0 grams(g), 7.75 millimoles (mmol)) in acetonitrile (CH₃CN; 50 milliliters(mL)) was added bis-N,O-trimethylsilylacetamide (BSA; 5.7 mL, 23.3 mmol)and the mixture was heated at 70° C. for 1 hour (h), resulting in aclear solution. After cooling to room temperature,4-methoxybenzene-1-sulfonyl chloride (1.8 g, 8.5 mmol) was added, andthe mixture was stirred for 24 h. The solvent was evaporated and theresidue was partitioned between ethyl acetate (EtOAc) and brine. Theorganic phase was dried over magnesium sulfate (MgSO₄), filtered, andevaporated to yield the product as a pale yellow solid (1.48 g, 64%): mp182-185° C.; ¹H NMR (300 MHz, CDCl₃) δ 8.40 (br s, 1H), 8.11 (d, J=5.9Hz, 1H), 8.04-7.98 (m, 2H), 7.02-6.96 (m, 2H), 5.77 (br s, 1H), 3.88 (s,3H); ESIMS m/z 300 ([M+H]⁺).

Step 2: Preparation of5-Fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidin-2(1H)-one(I-2)

To an 8-mL screw capped vial were added4-amino-5-fluoro-1-(4-methoxyphenylsulfonyl)pyrimidin-2(1H)-one (0.293g, 0.979 mmol), anhydrous potassium carbonate (K₂CO₃; 0.271 g, 1.96mmol), and N,N-dimethylformamide (DMF; 4 mL), followed by iodomethane(CH₃I; 0.208 g, 1.47 mmol). The reaction vessel was sealed, and thereaction mixture was warmed to 60° C. and stirred for 4 h. The reactionmixture was cooled to room temperature, diluted with EtOAc (20 mL), andwashed with water (H₂O; 3×10 mL). The organic phase was dried overMgSO₄, filtered, and the solvent was evaporated under reduced pressure.Purification by flash chromatography (silica gel (SiO₂), EtOAc/Hexanesgradient) afforded the title compound as a pale yellow solid (36milligrams (mg), 12%): mp 158-162° C.; ¹H NMR (400 MHz, DMSO-d₆) δ 8.01(d, J=9.22 Hz, 2H), 7.74 (d, J=5.27 Hz, 1H), 7.04 (d, J=9.23 Hz, 2H),3.90 (s, 3H), 3.31 (s, 3H); ESIMS m/z 314 ([M+H]⁺).

Step 3: Preparation of5-Fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (I-3)

A 25-mL screw capped vial was charged with5-fluoro-4-imino-1-(4-methoxyphenylsulfonyl)-3-methyl-3,4-dihydropyrimidin-2(1H)-one(80.4 mg, 0.257 mmol), trifluoroacetic acid (TFA; 16.0 mL, 215 mmol),and dimethylsulfide (94.0 μL, 1.28 mmol). The resulting solution wasallowed to stir at room temperature for 5.5 h and was then concentratedto dryness by rotary evaporation at 30° C. The crude material was thendissolved in a minimal amount of methanol (CH₃OH; ˜2 mL) and loaded ontoa 5 g normal phase solid load Isco cartridge, rinsing the source vialwith CH₃OH (3×1 mL). The solid cartridge was then dried under vacuum atroom temperature. After drying, the product was purified bychromatography (4 g SiO₂ column; 0 to 30% CH₃OH in dichloromethane(CH₂Cl₂) gradient). The material thus obtained was determined to be the4-methoxysulfonic acid salt of the desired product. The free base wasobtained by dissolving the material in CH₃OH (4 mL), adding MP-carbonateresin (345 mg, 3.03 mmol/g, 4.0 equiv), and allowing to stir at roomtemperature. After stirring for 20 h, the solid resin was filtered offand rinsed with CH₃OH (3×1 mL). After concentration under high vacuum,5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (35.2 mg, 96%)was obtained as a 95% pure white solid: mp 181-184° C.; ¹H NMR (400 MHz,DMSO-d₆) δ 7.48 (d, J=4.1 Hz, 1H), 3.22 (s, 3H); ¹³C NMR (101 MHz,DMSO-d₆) δ 152.19 (s), 151.86 (d, J=27.3 Hz), 136.73 (d, J=221.0 Hz),129.45 (d, J=26.0 Hz), 28.91 (s).

Example 2 Preparation of 4-methoxyphenyl5-fluoro-4-imino-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxylate(Compound 1)

(E)-trimethylsilyl N-(trimethylsilyl)acetimidate (157 mg, 0.774 mmol)was added to a mixture of5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (100 mg, 0.704mmol) and acetonitrile (1.0 mL) and heated at 70° C. for 30 min. Thesolution was cooled to room temperature and 4-methoxyphenylchloroformate (144 mg, 0.774 mmol) was added dropwise and the contentswere stirred overnight at room temperature. A precipitate had formed andwas collected on a frit and was washed with a small amount of ether togive the title compound as a white solid (45 mg, 22%), mp 136-137° C.;¹H NMR (400 MHz, DMSO-d₆) δ 8.91 (s, 1H), 8.04 (d, J=6.8 Hz, 1H), 7.23(d, J=9.0 Hz, 2H), 7.01 (d, J=9.0 Hz, 2H), 3.77 (s, 3H), 3.31 (s, 3H);¹³C NMR (101 MHz, DMSO) δ 157.34, 150.71, 150.40, 148.77, 145.93,143.55, 139.59, 137.32, 122.22, 116.54, 116.14, 114.52, 55.45, 29.20;ESIMS m/z 294 ([M+H]⁺).

Example 3 Preparation of (Z)-4-methoxyphenyl5-fluoro-4-(4-methoxyphenoxy)carbonyl)imino)-3-methyl-2-oxo-3,4-dihydropyrimidine-1(2H)-carboxylate(Compound 2)

Added (E)-trimethylsilyl N-(trimethylsilyl)acetimidate (215 mg, 1.06mmol) to a mixture of5-fluoro-4-imino-3-methyl-3,4-dihydropyrimidin-2(1H)-one (100 mg, 0.704mmol) and acetonitrile (1.0 mL) and heated at 70° C. for 30 min. Thesolution was cooled to room temperature and 4-methoxyphenylchloroformate (328 mg, 1.76 mmol) was added dropwise and the contentswere stirred overnight at room temperature. The mixture containingprecipitates was diluted with 2 mL of ether and filtered. The solid waswashed with water and air dried to give the title compound as a whitesolid (65 mg, 21%): mp 162-166° C.; ¹H NMR (400 MHz, CDCl₃) δ 7.95 (d,J=7.3 Hz, 4H), 7.14 (dd, J=15.7, 9.0 Hz, 24H), 6.93 (t, J=9.4 Hz, 18H),3.82 (d, J=6.7 Hz, 26H), 3.52 (s, 13H); ¹³C NMR (101 MHz, DMSO-d₆) δ157.95, 157.47, 156.86, 148.23, 145.42, 144.08, 143.47, 134.06, 122.27,122.14, 114.61, 114.49, 55.47, 55.40, 30.54; ESIMS m/z 444 ([M+H]⁺).

Example A Evaluation of Fungicidal Activity: Leaf Blotch of Wheat(Mycosphaerella graminicola; Anamorph: Septoria tritici; Bayer CodeSEPTTR)

Wheat plants (variety Yuma) were grown from seed in a greenhouse in 50%mineral soil/50% soil-less Metro mix until the first leaf was fullyemerged, with 7-10 seedlings per pot. These plants were inoculated withan aqueous spore suspension of Septoria tritici either prior to or afterfungicide treatments. After inoculation the plants were kept in 100%relative humidity (one day in a dark dew chamber followed by two tothree days in a lighted dew chamber) to permit spores to germinate andinfect the leaf. The plants were then transferred to a greenhouse fordisease to develop.

The following table presents the activity of typical compounds of thepresent disclosure when evaluated in these experiments. Theeffectiveness of the test compounds in controlling disease wasdetermined by assessing the severity of disease on treated plants, thenconverting the severity to percent control based on the level of diseaseon untreated, inoculated plants.

TABLE 1 Compound number and structure Com- Prepared as pound describedin No. Structure Example: Precursor(s): 1

2 As described 2

3 As described 3

2 4- methylphenyl chloroformate; I-3 4

2 phenyl chloroformate; I-3

TABLE 2 Compound number and analytical data Compound MP No. Appearance(° C.) Mass ¹H NMR ¹³C NMR 1 White 135.6-137.1 ESIMS ¹H NMR (DMSO- ¹³CNMR (DMSO- Solid m/z 294 d₆) δ 8.91 (s, 1H), d₆) δ 157.34, [M + H]+ 8.04(d, J = 6.8 Hz, 150.71, 150.40, 1H), 7.23 (d, J = 9.0 Hz, 148.77,145.93, 2H), 7.01 (d, J = 9.0 Hz, 143.55, 139.59, 2H), 137.32, 122.22,3.77 (s, 3H), 3.31 (s, 3H) 116.54, 116.14, 114.52, 55.45, 29.20 2 White161.8-165.6 ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (DMSO- Solid m/z 444 7.95 (d,J = 7.3 Hz, d₆) δ 157.95, [M + H]⁺ 1H), 7.14 (dd, J = 15.6, 157.47,156.86, 8.9 Hz, 4H), 148.23, 145.42, 6.93 (t, J = 9.2 Hz, 144.08,143.47, 4H), 3.82 (d, J = 6.7 Hz, 134.06, 122.27, 6H), 3.52 (s, 122.14,114.61, 3H) 114.49, 55.47, 55.40, 30.54 3 White 109.0-110.2 ESIMS ¹H NMR(CDCl₃) δ ¹³C NMR (CDCl₃) δ Solid m/z 278 7.87 (s, 1H), 152.36, 152.05,[M + H]⁺ 7.70 (d, J = 6.0 Hz, 1H), 149.69, 148.13, 7.22 (d, J = 8.3 Hz,146.31, 140.31, 2H), 7.14-7.06 (m, 138.01, 136.71, 2H), 3.50 (s, 3H),130.20, 120.64, 2.37 (s, 3H) 115.11, 114.70, 29.77, 20.91 4 White86.4-87.6 ESIMS ¹H NMR (CDCl₃) δ ¹³C NMR (CDCl₃) δ Solid m/z 264 7.88(s, 1H), 129.75, 126.91, [M + H]⁺ 7.71 (d, J = 6.0 Hz, 1H), 121.00,115.07, 7.48-7.40 (m, 2H), 114.65, 29.78 7.35-7.29 (m, 1H), 7.25-7.20(m, 2H), 3.51 (s, 3H)

In each case of Table 3 the rating scale is as follows:

% Disease Control Rating  76-100 A 51-75 B 26-50 C  0-25 D Not Tested E

TABLE 3 One-Day Protectant (1DP) and Three-Day Curative (3DC) Activityof Compounds vs. SEPTTR at 100 ppm SEPTTR SEPTTR Compound 100 PPM 100PPM No. 1DP 3DC 1 A A 2 A A 3 A A 4 A A

What is claimed is:
 1. A compound of Formula I:

wherein R¹ is —C(═O)OR⁴ or —C(═S)OR⁴; R² is C₁-C₆ alkyl, C₂-C₆ alkenyl,C₃-C₆ alkynyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl, C₁-C₆ aminoalkyl,C₂-C₆ alkylcarbonyl, arylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆alkylaminocarbonyl, —S(O)₂R⁵, phenyl or benzyl wherein each of thephenyl or the benzyl may be optionally substituted with 1-3 R⁵, or a 5-or 6-membered saturated or unsaturated ring containing 1-3 heteroatomswherein each ring may be optionally substituted with 1-3 R⁵; R³ isindependently H, C₁-C₆ alkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₁-C₆haloalkyl, C₁-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, arylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl, phenyl or benzyl wherein eachof the phenyl or the benzyl may be optionally substituted with 1-3 R⁵,or a 5- or 6-membered saturated or unsaturated ring containing 1-3heteroatoms, wherein each ring may be optionally substituted with 1-3R⁵; R⁴ is independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxyalkyl,C₂-C₆ alkylcarbonyl, phenyl or benzyl wherein each of the phenyl or thebenzyl may be optionally substituted with 1-3 R⁵, or a 5- or 6-memberedsaturated or unsaturated ring containing 1-3 heteroatoms, wherein eachring may be optionally substituted with 1-3 R⁵; R⁵ is independentlyhalogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,C₁-C₆ alkylthio, C₁-C₆ haloalkylthio, amino, C₁-C₆ alkylamino, C₂-C₆alkoxycarbonyl, or C₂-C₆ alkylcarbonyl, cyano, or nitro.
 2. Acomposition for the control of a fungal disease, a comprising acomposition for the control of at least one fungal disease, saidcomposition including a fungicidally effective amount of the compound ofFormula I and a phytologically acceptable carrier material.
 3. Thecomposition of claim 2 wherein the fungal disease is Septoria tritici.4. A method for the control and prevention of fungal attack on a plant,the method including the steps of: applying a fungicidally effectiveamount of at least one of the compounds of Formula I to at least onesurface selected from the group of surfaces selected from the groupconsisting of: a portion of a plant, an area adjacent to a plant, soilin contact with a plant, soil adjacent to a plant, any surface adjacentto a plant, any surface in contact with a plant, a seed, and equipmentused in agriculture.
 5. The method of claim 1, wherein the fungicidallyeffective amount Formula I is applied to a surface in the range of about0.01 g/m² to about 0.45 g/m² of Formula I.